Fungicidal composition



United States Patent FUNGICIDAL COMPOSITION No Drawing. ApplicationOctober 29, 1953,

Serial No. 389,159

26 Claims. (Cl. 260-102) This invention relates to novel metal rosinammonium phenoxide complex-metal carboxylic acid soap reaction products,and to fungicidal and insecticidal compositions containing the same.More particularly, the invention relates to such reaction products whichform solutions having a relatively light color, thereby extending thefields of use thereof.

In my copending application entitled Fungicidal Composition, Serial No.389,146, filed on even date herewith, I have described and claimed metalrosin ammonium phenoxide complex-metal carboxylic acid soap compoundswhich are produced by the reaction of a metal rosin ammonium phenoxidecomplex and a water insoluble metal soap of a carboxylic acid and whichpossess a high fungicidal activity on plants, textiles, paper, leather,wood, sealers, lacquers, etc. In the treatment of textiles, paper, etc.with these novel compounds or in the incorporation thereof in varnishes,clear lacquers, etc. where the presence of undesirable extraneous colorsis a problem, it has been found that many of these compounds tend toimpart an objectionally dark color to the treated material. This darkcolor is particularly troublesome where the metal of the rosin ammoniumphenoxide complex which is reacted with a water insoluble carboxylicacid soap, is copper. For example, a solution of my novel reactionproduct made from a copper rosin ammonium phenoxide complex imparts totextiles treated therewith a blue color. Where it is desired to impartto canvas a khaki color, this blue color creates a dyeing problem.

I have found that if the reaction between the metal rosin ammoniumphenoxide complex and the water insoluble carboxylic acid soap iscarried out in the presence of a quinoline there is obtained a novelreaction product which has an enhanced fungicidal eflicacy and whichgives a relatively light colored solution having little hiding power.For example, where before a deep blue colored solution was obtained,solutions of the novel products obtained by carrying out the aforesaidreaction in the presence of a quinoline are of a light green color andtextiles treated therewith can be dyed to any desired khaki shadereadily.

In general, the novel reaction products of the present invention areprepared by reacting a metal rosin ammonium phenoxide complex with awater insoluble soap of a carboxylic acid in the presence of aquinoline, at an elevated temperature at least sufficient to place thereactants into homogeneous solution. The metal of the complex may benickel, copper, cobalt, zinc, silver, iron, chromium, mercury or othermetal capable of forming a complex with ammonia. The quinoline may beany quinoline, substituted or unsubstituted, such as quinoline,isoquinoline, quinaldine, 4-chloroquinoline, 6-nitroquinoline,7nitroquinoline, 6-methoxyquinoline, S-methoxyquinoline,Z-hydroxyquinoline, 4-methyl-2-hydroxyquinoline, 4-hydroxyquinoline,2-methyl-4-hydroxyquinoline, 5-

hydroxyquinoline, 6-hydroxyquinoline, 7 -hydroxyquinoline,Shydroxyquinoline, etc. The preferred quinolines areisoqirinoline andS-hydroxyquinoline. The reaction 2,772,264 Patented Nov. 27, 1956 may becarried out at a temperature in the order of about 250 to 400 F. Lowertemperatures may be used, but at a sacrifice of time. Highertemperatures, up to the lowest decomposition temperature of thereactants, may be used, if desired.

The proportions of the metal rosin ammonium phenoxide complex and of thewater insoluble soap reactants may be varied widely, as desired. Thus,stoichiometrical proportions of these reactants or an excess of one withrespect to the other may be used. With respect to the quinoline, theproportions thereof may vary widely, from about 2% to 15% by weightbased on the weight of the phenoxide complex reactant.

The metal rosin ammonium phenoxide complex may be introduced as suchinto the reaction with the water insoluble soap and the quinoline or itmay be formed in situ in the reaction mix. The in situ reaction ispreferred. In the in situ reaction the rosin ammonium phenoxide may bepreformed or it, too, may be formed in situ. The in situ formation ofthe phenoxide is preferred. Thus, in the preferred procedure, thereaction products of the present invention are formed by the reaction ofa water insoluble soap, a quinoline, a rosin amine, a phenol and a watersoluble salt of a metal capable of forming a complex with ammonia.

The rosin ammonium phenoxide which may be used in accordance with thepresent invention may be made by reacting a rosin amine with a simple orsubstituted phenol as described in Patent No. 2,513,429, granted July 4,1950. The metal rosin ammonium phenoxide complex which may be used as areactant in accordance with the present invention may be made byreacting. a rosin ammonium phenoxide with a water soluble salt of ametal (nickel, cobalt, iron, aluminum, copper, zinc, mercury, silver,etc.) capable of forming a complex with ammonia. Examples of thesesoluble salts are copper acetate, zinc acetate, the acetates of theother named metals, and the formate, chloracetate, bromoacetate,chloride, sulfate, borate, carbonate, thiocyanate, etc., salts of metalscapable of forming complexes with ammonia.

Examples of the rosin amines which may be used to form the phenoxidereactant of the present invention include the rosin amines made fromwood or gum rosin or various modified wood or gum rosins, such asdehydrogenated (disproportionated) rosin, hydrogenated rosin, orpolymerized rosin. The rosin amines may also be the amines derived fromthe pure rosin acids in which abietyl amine is the amine derived fromabietic acid, dehydroabietyl amine is the amine derived fromdehydroabietic acid, dihydroabietyl amine is the amine derived fromdihydroabietic acid, and tetrahydroabietyl amine is the amine derivedfrom tetrahydroabietic acid. And they may be the secondary tertiaryrosin amines in which the hydrogens attached to the nitrogen arereplaced by lower alkyl and alkylol groups, such as methyldehydroabietyl amine, ethyl dehydroabietyl amine, dimethyldehydroabietyl amine, diethyl dehydroabietyl amine, isopropyldehydroabietyl amine, butyl dehydroabietyl amine, hydroxymethyldehydroabietyl amine, hydroxyethyl dehydroabietyl amine, anddi(hydroxyethyl) dehydroabietyl amine. Similar secondary and tertiaryrosin amines having the nucleus of abietic acid, dihydroabietic acid,tetrahydroabietic acid, and polymerized abietic acid may also be used,as may also the other amines referred to in the aforesaid patent.

Examples of phenols which may be used to form the phenoxide reactant ofthe present invention are phenol, ortho amyl phenol, octyl phenol, nonylphenol, ortho, meta and para cresol, para chloro meta cresol and otherchlorinated cresols, tertiary butyl meta cresol, resorcinol, pyrogallol,xylenol, para tolyl phenol, xylyl phenol,

menthyl phenol, cumyl phenol, beta naphthol, chlorinated phenols such asmonochlorophenol, dichlorophenol, dichlorophenol, trichlorophenol,tetrachlorophenol, pent-achlorophenol, nitrated phenols such asmononitrophenol, dinitrophenol, trinitrophenol, and nitrocresols, andthe like. i

The water insoluble soaps of carboxylic acids which are used asreactants in accordance with the present invention are water-insolublesoaps of a metal or a mixture of metals and a soap-forming acid or amixture of such acids. Thus, the soaps may be soaps of calcium, barium,magnesium, mercury, lead, cadmium, silver, thallium, manganese, cobalt,nickel, iron, copper, tin, aluminum and the like. .The preferred soapsare the copper, zinc and nickel soaps because the results obtained withthese soaps are superior to those obtainable with the othersoapsreferred to herein.

The soap-forming acids used in forming the aforesaid Water-insolublemetal soaps include monocarboxylic acids having at least 6 carbonatoms'in the carboxylic acid and being not otherwise substituted thanwith a hydrocarbon radical and the hydroxyl radical, such as caproicacid, caprylic acid, capric acid, lauric acid, myristic acid, palmisticacid, stearic acid, oleic acid, linoleic acid, linolenic acid,palmitoleic acid, melissic acid, hydroxystearic acid, ricinoleic acid,and the like, and mixtures thereof. The preferred soap-forming fattyacids or materials are those saturated and unsaturated higher aliphaticacids containing from twelve to eighteen carbon atoms, and rosin. Othersoap-forming fatty acids which may be used in forming the metal soapsused in accordance with the present invention are the mixed higher fattyacids derived from animal or vegetable sources such as, for example,sardine and other fish oils, lard, coconut oil, sesame oil, soybean oil,tung oil, corn oil or partially or completely hydrogenated derivativesof such oils, fatty acids derived from carnauba, spermaceti, beeswax,candelilla wax and like waxes, and carboxylic acids derived frompetroleum or other hydrocarbons. Othersoap-forming acids which may beused are naphthenic acid, tall oil fatty acids, and hydroaromatic acidssuch as abietic acid and the like.

The following examples are illustrative of the preferred method whichmay be used to form the reaction products of the present invention. Inthe examples the term parts refers to parts by weight.

Example I 70 parts of magnesium acetate were added with stirring to 100parts of 2-ethylhexoic acid at a temperature of 350 to-420 F. Theheating and agitation were continued until the acetic acid liberated bythe reaction was vaporized. The addition of 5 parts 8-hydroxyquinoline,100 parts of nonyl phenol and 100 parts of dehydroabietyl amine causedthe temperature to drop to 260 F.- At this point 55 parts of copperacetate were added and the temperature was raised to 340 R, where it wasmaintained for 15 minutes, whereupon a clear solution was obtained andheating discontinued. When the temperature dropped to 175 F., 235 partsof xylol were added. The resulting composition was liquid at roomtemperature.

The composition of Example 1 was tested to determine its fungicidalactivity by treating duck samples with a xylol solution containing 5% ofthe reaction product, as follows:

Samples of 10 oz. specification army duck were cut into 10" x 30' piecesand the pieces were washed in soap suds, rinsed and dried. The driedpieces were passed through the testing solution so that completepenetration was obtained. They were then passed through a wringer toremove the excess solution. Approximately a 50% wet-pickup was obtained.The treated fabric pieces werethen dried for 24 hours to obtain complete4 solvent release. The dried fabric pieces had a light green color.

The treated and dried pieces of duck were leached for 24 hours inrunning water and buried horizontally in a well composted soilconsisting of 50% black loam and 50% pre-rotted manure, one-half inchbelow the soil surface. The moisture content of the soil was maintainedat approximately 30-50%.

After 28 days incubation in the soil bed, the fabric pieces were removedand examined. There was no evidence of degradation found in the treatedfabric pieces after burial and they had retained their original handcharacteristics. A control 10" x 30" sample of the aforesaid army duckcontaining no treatment was buried at the same time as the treatedpieces and under the same conditions. The control was completelydestroyed, being in the form of small deteriorated pieces at theconclusion of the 28 day test period.

Prior to impregnating the piece of duck with the solution of Example 1,it and the untreated piece of duck were tested for tensile strengths ona 500 lb. vertical Scott tester. Each had a tensile strength of 296 lbs.After the 28 day burial period the treated duck and the control piecewere removed from the soil, washed thoroughly in warm water to removeall soil particles and airdried at room temperature. Tensile strength onthe treated piece was then taken on the same Scott tester. It had atensile strength of 298 lbs. The control piece was removed from the'soilin small deteriorated pieces which had lost their fabric strength andhence were not tested. Each of these small pieces was badly stained. Incontrast the treated piecewas substantially free from stain.

Example 2 Example 1 was repeated except that parts of phenol were usedin lieu of the nonyl phenol. A test solution and fabric pieces were madeup and tested against an untreated fabric control piece, as described.The treated pieces showed no sign of degradation and noloss of hand,whereas the control piece had completely deteriorated.

Example 4 Example 1 was repeated except that 100 parts of dihydroabietylamine were used in lieu of the dehydroabietyl amine and 30 parts ofquinoline were used in lieu of the 8-hydroxyquinoline. A test solutionand fabric pieces were made up and tested against an untreated fabriccontrol piece, as described. The treated pieces showed no sign ofdegradation and no loss of hand, whereas the control piece hadcompletely deteriorated.

Example 5 Example 1 was repeated except that 30 parts of 8'methoxyquinoline were used in lieu of the 8-hydroxyquinoline. A testsolution and fabric pieces were made up and tested against an untreatedfabric control piece, as described. The treated pieces showed no sign ofdegradation and no loss of hand, whereas the control piece hadcompletely deteriorated.

Example 6 Example 1 was repeated except that a corresponding amount ofnickel 2-ethylhexoate was used in lieu of the soap of Example 1 and 30parts of 4-ch1oroquinoline were used in lieu of the 8-hydroxyquinoline.A test solution and fabric. pieces were made up and tested against anuntreated fabric: control piece, asrdescribed. The treated pieces showedno sign of degradation and no loss, of

hand, whereas the control: piece had comletely dete riorated.

Examples .7, 8; 9 and 10 Example 1 was repeated except that 55 parts of.zinc acetate were used in lieuof the copper acetate. Example 1 wasrepeated except that 55 parts of mercury carbonate were used in lieu ofthe copper acetate. Example 1 was repeated'except that 55 parts ofnickel chloroacetate were used'in lieu ofthe copper acetate. Examplelwas repeated exceptthat 55 parts of silver acetate were usedin lieu ofthe. copper acetate. Test solutions of these double salts and fabricpieces treated therewith were made up and tested against an untreatedfabric control piece, as described. The treated pieces showed no sign ofdegradation and no loss of handjwhereas the control piece had completelydeteriorated.

The reaction products of each of Examples 1 to 10, inclusive, in theform of the solutions described, were individually applied'towoodsamples l" x 3 and leather squares 2 x 2" by soaking under vacuumfor 20 minutes and drying for 6 hours. The treated specimens anduntreated control specimens of similar dimensions were placed on asterile nutrient agar medium with a pH of 5 5, which was used for thesubstratum in the petridishes in which the specimens were placed. Eachtreated specimen and a control specimen were placed in a singlepetridish. The specimens in each-of these dishes were sprayed with" aspore suspension of the following organisms and incubated at 30 C. for14 days: Chaetomium globosum, Pefnicillium citrinum, Aspergillus niger,Aspergillus ferreus, Iri'clioderma viz-isle, andA'spergillus flavus.

At the conclusion of this test period it was found that fungi weregrowing over the entire surface of the leather and wood controlspecimens and that no growth existed on the treated wood andleatherspecimens.

The reaction products of the present invention can be used" to treattextiles, paper, leather and. the like by impregnating or coating thesematerials with a solution or dispersion of the reaction product in asuitable vehicle. Thus, the solutions described above may be usedtotreat these materials. These solutions may be compounded with resins,animal, vegetable and fish oils, plasticizers, fiameproofing agents,driers, antioxidants and the like, in accordance with known techniques,to impart) to the solutions desired properties. For example,characteristics such as spread and flow of 'these solutions maybe'modified' by the addition thereto of a fatty acid such as l'auricacid; ol'eic acid', linseed oilfatty acids, hempseed oilfatty acids andlike fatty acids having from 8 to 20' carbon atoms in the chain, and ofa fatty acid glyceride, either raw or treated, such as raw or bodiedlinseedoil', China wood oil, castor oil, dehydrated castor oil,.and thelike. Compatible natural and synthetic resins such as rosin,phenol-aldehyde resins,urea-aldehyderesins, vinyl resins and the. like,or compatible cellulose derivatives such as nitrocellulose, cellulose,cellulose acetate, ethyl cellulose and thelike. may be. incorporated inthe: solutions invarying proportions tomeet any desired needs;

Plasticizers such as glycol, glyceriue, pentaerythritol, sorbitol,mannitol and other compatible plasticizers may the added to thesolutions. Suitable anti-oxidants which may be added to the solution arephenyl salicylate, tertiary butyl catechol and guaiacol, and suitabledriers are zinc naphthen-ate, lead naphthenate, cobalt naphthenate andzinc octoate.

If it is desired to impart water proof properties to the solutions ofthe reaction products otthe present invention, various waxes such asparaffin wax, beeswax, carnauba wax, sperrnaceti wax, synthetic waxes,and the like, may be incorporated in the solutions in varyingproportions to meet the desired needs.

By a proper choice of the solvents for the reaction products of thepresent invention and of suitable modifyingyagents, the resulting liquidcompositions may becon trolledgastto consistency, drying time, how,penetration, and 1: the like;

Other solvents for the reaction products-ofthe pres: ent invention aretoluol, benzol, carbon tetrachloride, mineral spirits, naphtha, acetone,and the like.

Compositions containing reaction products of the presentinvention notonly inhibit the growth of fungus. organisms butmay also kill theactivity of all existing 'fungus growth on contact. Textiles, leather,wood, resins, etc., which have been treated "with the reaction productsof the present invention are not attacked to any appreciable extent bysoil animal life and these treated materials resist the action ofbacteria and insects. The reaction products of the present inventionlend= themselves for use as insecticides, in either dry or liquid form,and for preventing and combating diseases of plant life, both thosediseases which attack the parts of plants above ground and diseases suchas rot which attack underground parts of the plants. In dry form theactive ingredient is mixed with an inert diluent such as bentoni-te,kieselguhr, talc, etc.

While the present invention has been described in connection withcertain specific examples of methods of making thereaction products, itis obvious'thatmy. invention is not-to be construed as limited to thespecific materials disclosed in these examples or to. the details of themethods set forth therein, since changes in materi-als, proportion andmethod details may be made without departing from the scope of myinvention as defined in the appended claims.

I claim:

1 The method offorming a composition of, matter. comp-rising heating atan elevated temperature suffi'cient to place the reactantsintohomogeneous solution, said temperature being: below the lowestdecomposition tem perature of the reactants, a metal rosin ammoniumphenoxide complex the: metal of said complex being from a-wa-ter-solublemetal capable of forming a complex with.

ammonia, a, water-insoluble mono-carboxylic acid soap having at. least 6carbon atoms in the carboxylic acid, said. carboxylic acid beingnototherwise substituted than. with a; hydrocarbon radical and the hydroxylradical and a quinoline,

2. The product produced by the. method of claim 1.

3. The method of forming a composition of matter: comprising heating atan elevated temperature sufiicient to place the reactants into;homogeneous solution, said temperature being. below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a water-insoluble mono-carboxylic acid soap having.at least 6 carbon atoms in the canboxylic acid, said carboxylic acidbeing not otherwise substituted than with a hydrocarbon. radical and thehydroxyl radical and; a quinoline selected from the class consistingfrom quinoline isoquinoline, quina-ldine, a hydroxyquinoline,nitroquinoline, chloroquino-line and methoxyquinoline.

4; The product produced by the method of claim 3 5. 'Phe method offorming a composition of matter comprising heating atan elevatedtemperature sufiicient to place the reactants into homogeneous solution,said temperature being 'below the lowest decomposition temperature ofthe reactants, copper rosin ammonium phenoxide complex, a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in thecarboxylic acid, said carboxylic acid being not otherwise substitutedthan with a hydrocarbon radical and the hydroxyl radical andS-hydroxyquinoline.

6. The product produced by the method of claim 5.

7. The method of forming a composition of matter comprising heating atan elevated temperature suihcient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a water-insoluble mono-carboxylic acid soap having atleast 6 carbon atoms in the carboxylic acid, said carboxylic acid beingnot otherwise substi- 'tuted than with a hydrocarbon radical and thehydroxyl radical and isoquinoline.

8. The product produced by the method of claim 7.

9. The method of forming :a composition of matter comp-rising heating atan elevated temperature suflieient ,to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a water-insoluble mono-carboxylic acid so'ap havingat least 6 carbon atoms in the carboxylic acid, said carboxylic acidbeing not otherwise substituted than with a hydrocarbon radical and thehydroxyl radical and quinoline.

10. The product produced by the method of claim 9.

11. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a water-insoluble mono-carboxylic acid soap having atleast 6 carbon atoms in the carboxylic acid, said carboxylic acid beingnot otherwise substituted than with a hydrocarbon radical and thehydroxyl radical and hydroxyquinoline.

12. The method of forming a composition of matter comp-rising heating atan elevated temperature suflicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a water-insoluble mono-oarboxyli acid soap having atleast 6 carbon atoms in the carboxylic acid, said carboxylic acid beingnot otherwise substituted than with a hydrocarbon radical and thehydroxyl radical and quinaldine.

13. The method of forming a composition of matter comprising heating atan elevated temperature sufficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a water-insoluble mono-carboxylic acid soap having atleast 6 carbon atoms in the carboxylic acid, said carboxylic acid beingnot otherwise substituted than with a hydrocarbon radical and thehydroxyl radical and 4-chloroquinoline.

14. The method of forming a composition of matter comprising heating atan elevated temperature sufficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a magnesium carboxylic acid soap and a quinolineselected from the class consisting from quinoline, isoquinoline,quinaldine, a hydroxyquinoline, ni troquinoline, chloroquinoline andmethoxyquinoline.

"15. The product produced by the method of claim l4.

16. The method of forming a composition of matter comprising heating atan elevated temperature suflicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a magnesium carboxylic acid soap andS-hydroxyquinoline.

17. The product produced by the method of claim 16.

18. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperat-ure of the reactants, copper rosin ammoniumphenoxide complex, a magnesium carboxylic acid soap and isoquinoline.

19. The product produced by the method of claim 18.

20. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex, a magnesium carboxylic acid soapand quinoline.

21. The product produced by the method of claim 20.

22. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperalture of the reactants, copper rosin ammoniumphenoxide complex, a magnesium carboxylic acid soap and anhydroxyquinoline.

23. The method of forming a composition of matter comprising heating atan elevated temperature sutficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the react-ants, a rosin amine, a phenol, awater-soluble salt of a metal capable of forming a complex with ammonia,a water-insoluble mono-carboxylic acid soap having at least 6 carbonatoms in the carboxylic acid, said carboxylic acid being not otherwisesubsti- Ituted than with a hydrocarbon radical and the hydroxyl radicaland a quinoline selected from the class consisting from quinoline,isoquinoline, quinaldine, a hydroxyquinoline, nit-roquinoline,chloroquinoline and methoxyquinoline.

24. The method of forming a composition of matter comprising heating atan elevated temperature sufficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, dehydroabietyl amine, nonylphenol, copper acetate, magnesium 2-ethylhexoate and 8-hydroxyquinoline.

25. The product produced by the method of claim 24.

26. The method of forming a composition of matter comprising heating atan elevated temperature sufficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, dehydroabietyl amine, nonylphenol, copper acetate, magnesium 2-ethylhexoate and isoquinoline.

References Cited in the file of this patent UNITED STATES PATENTS2,490,924 Schertz Dec. 13, 1949 2,490,925 Schertz Dec. 13, 19492,492,939 Schertz Dec. 27, 1949 2,513,429 Rosher July 4, 1950 2,623,870Sanders Dec. 30, 1952

1. THE METHOD OF FORMING A COMPOSITION OF MATTER COMPRISING HEATING ATAN ELEVATED TEMPERATURE SUFFICIENT TO PLACE THE REACTANTS INTOHOMOGENEOUS SOLUTION, SAID TEMPERATURE BEING BELOW THE LOWESTDECOMPOSITION TEMPERATURE OF THE REACTANTS, A METAL ROSIN AMMONIUMPHENOXIDE COMPLEX THE METAL OF SAID COMPLEX BEING FROM A WATER-INSOLUBLEMETAL CAPABLE OF FORMING A COMPLEX WITH AMMONIA, A WATER-INSOLUBLEMONO-CARBOXYLIC ACID SOAP HAVING AT LEAST 6 CARBON ATOMS IN THECARBOXYLIC ACID, SAID CARBOXYLIC ACID BEING NOT OTHERWISE SUBSTITUTEDTHAN WITH A HYDROCARBON RADICAL AND THE HYDROXYL RADICAL AND AQUINOLINE.